College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China.
Chem Asian J. 2012 Jun;7(7):1488-501. doi: 10.1002/asia.201101063. Epub 2012 Mar 29.
Active methylene compounds are a major class of reaction partners for C-C bond formation with sp(2) C-X (X = halide) fragments. As one of the most-classical versions of the Ullmann-type coupling reaction, activated-methylene-based C-C coupling reactions have been efficiently employed in a large number of syntheses. Although this type of reaction has long relied on noble-metal catalysis, the renaissance of copper catalysis at the end of last century has led to dramatic developments in Ullmann C-C coupling reactions. Owing to its low cost, abundance, as well as excellent catalytic activity, the exceptional atom economy of copper catalysis is gaining widespread attention in various organic synthesis. This review summarizes the advances in copper-catalyzed intermolecular and intramolecular C-C coupling reactions that use activated methylene species as well as in tandem reactions that are initiated by this transformation.
活性亚甲基化合物是 sp(2) C-X（X = 卤素）片段与 C-C 键形成的主要反应伙伴之一。作为最经典的 Ullmann 型偶联反应之一，基于活性亚甲基的 C-C 偶联反应已被有效地应用于大量合成中。尽管这种类型的反应长期依赖于贵金属催化，但上个世纪末铜催化的复兴导致了 Ullmann C-C 偶联反应的显著发展。由于铜催化具有成本低、丰富、活性好的特点，其在各种有机合成中具有出色的原子经济性，引起了广泛关注。本文综述了使用活性亚甲基物种的铜催化的分子间和分子内 C-C 偶联反应以及由这种转化引发的串联反应的进展。
